Colorant compounds

ABSTRACT

Disclosed is a compound of the formula 
                         
and dimers thereof, wherein R, R′, X, (Y) m , and (Z) n  are as defined herein. The compounds are useful as colorants, particularly in applications such as phase change inks.

This application is a divisional of U.S. patent application Ser. No.11/732,796 filed Apr. 4, 2007, now pending, U.S. Publication NumberUS-2008-0249290, the disclosure of which is totally incorporated hereinby reference.

CROSS-REFERENCES TO COPENDING APPLICATIONS

Cross-reference is made to the following co-pending applications:

Co-pending U.S. patent application Ser. No. 11/732,795, filed Apr. 4,2007, entitled “Phase Change Inks Containing Colorant Compounds,” withthe named inventor Jeffery H. Banning, the disclosure of which istotally incorporated herein by reference, discloses in embodiments aphase change ink composition comprising a phase change ink carrier and adimeric colorant compound.

Co-pending U.S. patent application Ser. No. 11/732,745, filed Apr. 4,2007, entitled “Colorant Compounds,” with the named inventors Jeffery H.Banning, et al., the disclosure of which is totally incorporated hereinby reference, discloses compounds of the formula

and dimers thereof.

Co-pending U.S. patent application Ser. No. 11/732,811, filed Apr. 4,2007, entitled “Phase Change Inks Containing Colorant Compounds,” withthe named inventors Jeffery H. Banning, et al., the disclosure of whichis totally incorporated herein by reference, discloses a phase changeink composition comprising a phase change ink carrier and a colorantcompound.

BACKGROUND

The present disclosure is generally related to colorant compounds. Morespecifically, the present disclosure is directed to colorant compoundsparticularly suitable for use in hot melt or phase change inks. Inembodiments, the present disclosure is directed to dimeric azopyrazolone colorant compounds particularly suitable for use in hot meltor phase change inks. One embodiment of the present disclosure isdirected to a compound of the formula

and dimers thereof, wherein R and R′ are each independently selectedfrom (i) an alkyl group, (ii) an alkylene group, (iii) an arylene group,(iv) an arylalkylene group, (v) an alkylarylene group, (vi) analkyleneoxy group, (vii) an aryleneoxy group, (viii) an arylalkyleneoxygroup, (ix) an alkylaryleneoxy group, (x) a polyalkyleneoxy group, (xi)a polyaryleneoxy group, (xii) a polyarylalkyleneoxy group, (xiii) apolyalkylaryleneoxy group, (xiv) a heterocyclic group, (xv) a silylenegroup, (xvi) a siloxane group, (xvii) a polysilylene group, (xviii) apolysiloxane group, or (xix) hydrogen, provided both R and R′ cannot behydrogen; and

wherein X is a (i) direct bond, (ii) an oxygen atom, (iii) a nitrogenatom, (iv) a sulfur atom, (v) a group of the formula —NR₄₀— wherein R₄₀is a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group,or an alkylaryl group, (vi) or a group of the formula —CR₅₀R₆₀—; whereinR₅₀ and R₆₀ each, independently of the other, is a hydrogen atom, analkyl group, an aryl group, an arylalkyl group, or an alkylaryl group;and

wherein (Y)_(m) and (Z)_(n) are each independently optionally presentand wherein (Y)_(m) and (Z)_(n) are each independently selected from i)a hydrogen atom, (ii) a halogen atom, (iii) a nitro group, (iv) an alkylgroup, (v) an aryl group, (vi) an arylalkyl group, (vii) an alkylarylgroup, (viii) a group of the formula

wherein R₇₀ is an alkyl group, an aryl group, an arylalkyl group, analkylaryl group, an alkoxy group, an aryloxy group, an arylalkyloxygroup, an alkylaryloxy group, a polyalkyleneoxy group, a polyaryleneoxygroup, a polyarylalkyleneoxy group, a polyalkylaryleneoxy group, aheterocyclic group, a silyl group, a siloxane group, a polysilylenegroup, or a polysiloxane group, (ix) a sulfonyl group of the formula—SO₂R₈₀ wherein R₈₀ is a hydrogen atom, an alkyl group, an aryl group,an arylalkyl group, an alkylaryl group, an alkoxy group, an aryloxygroup, an arylalkyloxy group, an alkylaryloxy group, a polyalkyleneoxygroup, a polyaryleneoxy group, a polyarylalkyleneoxy group, apolyalkylaryleneoxy group, a heterocyclic group, a silyl group, asiloxane group, a polysilylene group, or a polysiloxane group, or (x) aphosphoryl group of the formula —PO₃R₉₀ wherein R₉₀ is a hydrogen atom,an alkyl group, an aryl group, an arylalkyl group, an alkylaryl group,an alkoxy group, an aryloxy group, an arylalkyloxy group, analkylaryloxy group, a polyalkyleneoxy group, a polyaryleneoxy group, apolyarylalkyleneoxy group, a polyalkylaryleneoxy group, a heterocyclicgroup, a silyl group, a siloxane group, a polysilylene group, or apolysiloxane group.

and in (Y)m, m is an integer from about 0 to about 4, or about 1 toabout 3, or about 1 to about 2, and in (Z)n, n is an integer from about0 to about 4, or about 1 to about 3, or about 2 to about 3.

In general, phase change inks (sometimes referred to as “hot melt inks”)are in the solid phase at ambient temperature, but exist in the liquidphase at the elevated operating temperature of an ink jet printingdevice. At the jet operating temperature, droplets of liquid ink areejected from the printing device and, when the ink droplets contact thesurface of the recording substrate, either directly or via anintermediate heated transfer belt or drum, they quickly solidify to forma predetermined pattern of solidified ink drops. Phase change inks havealso been used in other printing technologies, such as gravure printing,as disclosed in, for example, U.S. Pat. No. 5,496,879 and German PatentPublications DE 4205636AL and DE 4205713AL, the disclosures of each ofwhich are totally incorporated herein by reference.

Phase change inks for color printing typically comprise a phase changeink carrier composition which is combined with a phase change inkcompatible colorant. In a specific embodiment, a series of colored phasechange inks can be formed by combining ink carrier compositions withcompatible subtractive primary colorants. The subtractive primarycolored phase change inks can comprise four component dyes, namely,cyan, magenta, yellow and black, although the inks are not limited tothese four colors. These subtractive primary colored inks can be formedby using a single dye or a mixture of dyes. For example, magenta can beobtained by using a mixture of Solvent Red Dyes or a composite black canbe obtained by mixing several dyes. U.S. Pat. No. 4,889,560, U.S. Pat.No. 4,889,761, and U.S. Pat. No. 5,372,852, the disclosures of each ofwhich are totally incorporated herein by reference, teach that thesubtractive primary colorants employed can comprise dyes from theclasses of Color Index (C.I.) Solvent Dyes, Disperse Dyes, modified Acidand Direct Dyes, and Basic Dyes. The colorants can also includepigments, as disclosed in, for example, U.S. Pat. No. 5,221,335, thedisclosure of which is totally incorporated herein by reference. U.S.Pat. No. 5,621,022, the disclosure of which is totally incorporatedherein by reference, discloses the use of a specific class of polymericdyes in phase change ink compositions.

Phase change inks have also been used for applications such as postalmarking, industrial marking, and labeling.

Phase change inks are desirable for ink jet printers because they remainin a solid phase at room temperature during shipping, long term storage,and the like. In addition, the problems associated with nozzle cloggingas a result of ink evaporation with liquid ink jet inks are largelyeliminated, thereby improving the reliability of the ink jet printing.Further, in phase change ink jet printers wherein the ink droplets areapplied directly onto the final recording substrate (for example, paper,transparency material, and the like), the droplets solidify immediatelyupon contact with the substrate, so that migration of ink along theprinting medium is prevented and dot quality is improved.

Compositions suitable for use as phase change ink carrier compositionsare known. Some representative examples of references disclosing suchmaterials include U.S. Pat. No. 3,653,932, U.S. Pat. No. 4,390,369, U.S.Pat. No. 4,484,948, U.S. Pat. No. 4,684,956, U.S. Pat. No. 4,851,045,U.S. Pat. No. 4,889,560, U.S. Pat. No. 5,006,170, U.S. Pat. No.5,151,120, U.S. Pat. No. 5,372,852, U.S. Pat. No. 5,496,879, EuropeanPatent Publication 0187352, European Patent Publication 0206286, GermanPatent Publication DE 4205636AL, German Patent Publication DE 4205713AL,and PCT Patent Application WO 94/04619, the disclosures of each of whichare totally incorporated herein by reference. Suitable carrier materialscan include paraffins, microcrystalline waxes, polyethylene waxes, esterwaxes, fatty acids and other waxy materials, fatty amide containingmaterials, sulfonamide materials, resinous materials made from differentnatural sources (tall oil rosins and rosin esters, for example), andmany synthetic resins, oligomers, polymers, and copolymers.

U.S. Pat. No. 6,576,747 of Rina Carlini et al., entitled “Processes forPreparing Dianthranilate Compounds and Diazopyridone Colorants,” whichis hereby incorporated by reference herein in its entirety, discloses aprocess for preparing dianthranilate compounds which comprises (a)admixing reactants as follows: (1) a diol of the formula R1(OH)2,wherein R1 is an alkylene group having at least about 20 carbon atoms,and wherein the —OH groups are primary or secondary, (2) isatoicanhydride, present in an amount of at least about 2 moles of isatoicanhydride per every one mole of diol, (3) a catalyst which is1,4-diazabicyclo [2,2,2]octane, N,N,N′,N′-tetramethylethylene diamine,or a mixture thereof, said catalyst being present in an amount of atleast about 0.2 mole of catalyst per every one mole of diol, and (4) asolvent; and (b) heating the mixture thus formed to form adianthranilate compound of the formula

Also disclosed is a process for preparing diazopyridone colorants whichcomprises (I) preparing a dianthranilate compound by the aforementionedmethod, (II) reacting the dianthranilate compound with nitrosylsulfuricacid to form a diazonium salt, and (III) reacting the diazonium saltwith a pyridine compound to form a diazopyridone compound.

U.S. Pat. No. 6,713,614 of Rina Carlini et al., entitled “Dimeric AzoPyridone Colorants,” which is hereby incorporated by reference herein inits entirety, discloses compounds of the formula

The compounds are useful as colorants, particularly in applications suchas phase change inks.

U.S. Pat. No. 6,663,703 of Bo Wu et al., entitled “Phase Change InksContaining Dimeric Azo Pyridone Colorants,” which is hereby incorporatedby reference herein in its entirety, discloses a phase change inkcomposition comprising a phase change ink carrier and a colorantcompound of the formula

U.S. Pat. No. 6,755,902 of Jeffrey H. Banning et al. entitled “PhaseChange Inks Containing Azo Pyridone Colorants” which is herebyincorporated by reference herein in its entirety, discloses a phasechange ink composition comprising a phase change ink carrier and acolorant compound of the formula

U.S. Pat. No. 6,590,082 of Jeffrey H. Banning et al. entitled “AzoPyridone Colorants,” which is hereby incorporated by reference herein inits entirety, discloses compounds of the formula

The compounds are useful as colorants, particularly in applications suchas phase change inks.

U.S. Pat. No. 6,696,552 of James D. Mayo et al. entitled “″Process forPreparing Substituted Pyridone Compounds,” which is hereby incorporatedby reference herein in its entirety, discloses a process for preparingsubstituted pyridone compounds which comprises (a) admixing in theabsence of a solvent (1) an amine of the formula R1-NH₂ wherein R1 is analkyl group, an aryl group, an arylalkyl group, or an alkylaryl group,and (2) a first ester of the formula

wherein R₂ is an electron withdrawing group and R₃ is an alkyl group;(b) heating the mixture containing the amine and the first ester to forman intermediate compound of the formula

(c) admixing the intermediate compound with (1) a base and (2) a secondester of the formula

wherein R₄ is an alkyl group, an aryl group, an arylalkyl group, or analkylaryl group and R₅ is an alkyl group, said second ester beingpresent in a molar excess relative to the intermediate compound, saidbase being present in a molar excess relative to the intermediatecompound, and (d) heating the mixture containing the intermediatecompound, the second ester, and the base to form a pyridone compound ofthe formula

or a salt thereof. Also disclosed is a process for preparingdiazopyridone colorants which comprises preparing a pyridone compound bythe above process and reacting the pyridone compound with a diazoniumsalt to form a diazopyridone compound.

U.S. Pat. No. 6,576,748 of Rina Carlini et al. entitled “Method forMaking Dimeric Azo Pyridone Colorants,” which is hereby incorporated byreference herein in its entirety, discloses a process for preparing adiazopyridone compound which comprises (a) preparing a first solutioncomprising (1) either (A) a dianiline of the formula

or (B) an aniline of the formula

and (2) a first solvent mixture comprising (I) a solvent, (II) aceticacid, and (III) an optional second acid, said acetic acid being presentin the solvent mixture in an amount of at least about 95 percent byweight of the solvent mixture, said first solution being at atemperature of about +15° C. or lower; (b) adding to the first solutionnitrosylsulfuric acid, thereby forming a diazonium salt either (A) ofthe formula

or (B) of the formula

(c) preparing a second solution comprising (1) a second solvent mixturecomprising water and an organic solvent soluble in or miscible in water,(2) either (A) a pyridone of the formula

or (B) a dipyridone of the formula

(3) a base present in an amount of at least about 3 molar equivalents ofbase per mole of pyridone moiety, and (4) an optional buffer salt, and(d) combining either (A) the second solution containing the dianilineand the first solution containing the pyridone, or (B) the secondsolution containing the aniline and the first solution containing thedipyridone to form a third solution and effect a coupling reaction toform a diazopyridone compound either (A) of the formula

or (B) of the formula

U.S. Pat. No. 6,646,111 of Rina Carlini et al. entitled “Dimeric AzoPyridone Colorants,” which is hereby incorporated by reference herein inits entirety, discloses compounds of the formula

The compounds are useful as colorants, particularly in applications suchas phase change inks.

U.S. Pat. No. 6,673,139 of Bo Wu et al. entitled “Phase Change InksContaining Dimeric Azo Pyridone Colorants,” which is hereby incorporatedby reference herein in its entirety, discloses a phase change inkcomposition comprising a phase change ink carrier and a colorantcompound of the formula

While known compositions and processes are suitable for their intendedpurposes, a need remains for new colorant compositions, for example newyellow to orange colorant compositions. In addition, a need remains foryellow to orange colorant compositions particularly suitable for use inphase change inks. Further, a need remains for yellow to orangecolorants with desirable thermal stability. Additionally, a need remainsfor yellow to orange colorants that exhibit minimal undesirablediscoloration when exposed to elevated temperatures. There is also aneed for yellow to orange colorants that exhibit a desirable brilliance.In addition, there is a need for yellow to orange colorants that exhibita desirable hue. Further, there is a need for yellow to orange colorantsthat are of desirable chroma. Additionally, there is a need for yellowto orange colorants that have desirably high lightfastnesscharacteristics. A need also remains for yellow to orange colorants thathave a desirably pleasing color. In addition, a need remains for yellowto orange colorants that exhibit desirable solubility characteristics inphase change ink carrier compositions. Further, a need remains foryellow to orange colorants that enable phase change inks to be jetted attemperatures of over 135° C. while maintaining thermal stability.Further, a need remains for yellow to orange colorants for use in solidink printers that operate with lower print head temperatures much lowerthan 135° C. as well as in ultraviolet radiation curable systems.Additionally, a need remains for yellow to orange colorants that enablephase change inks that generate images with low pile height. There isalso a need for yellow to orange colorants that enable phase change inksthat generate images that approach lithographic thin image quality. Inaddition, there is a need for yellow to orange colorants that exhibitoxidative stability. Further, there is a need for yellow to orangecolorants that do not precipitate from phase change ink carriers.Additionally, there is a need for yellow to orange colorants that donot, when included in phase change inks, diffuse into adjacently printedinks of different colors. A need also remains for yellow to orangecolorants that do not leach from media such as phase change ink carriersinto tape adhesives, paper, or the like. In addition, a need remains foryellow to orange colorants that, when incorporated into phase changeinks, do not lead to clogging of a phase change ink jet printhead.Further, there is a need for yellow to orange colorants that enablephase change inks that generate images with sharp edges that remainsharp over time. Additionally, there is a need for yellow to orangecolorants that enable phase change inks that generate images whichretain their high image quality in warm climates. Further, there is aneed for yellow to orange colorants that enable phase change inks thatgenerate images of desirably high optical density. Additionally, thereis a need for yellow to orange colorants that, because of their goodsolubility in phase change ink carriers, enable the generation of imagesof low pile height without the loss of desirably high optical density. Aneed also remains for yellow colorants that enable the use ofsubstantially reduced amounts of colorant in, for example, an inkwithout decreasing the color and the spectral properties (L*a*b*) of theink or jeopardizing the optical density or color of the prints generatedwith the ink. A need also remains for yellow to orange colorants thatenable cost-effective inks.

The appropriate components and process aspects of the each of theforegoing may be selected for the present disclosure in embodimentsthereof.

SUMMARY

The present disclosure is directed to a compound of the formula

wherein R and R′ are each independently selected from (i) an alkylgroup, (ii) an alkylene group, (iii) an arylene group, (iv) anarylalkylene group, (v) an alkylarylene group, (vi) an alkyleneoxygroup, (vii) an aryleneoxy group, (viii) an arylalkyleneoxy group, (ix)an alkylaryleneoxy group, (x) a polyalkyleneoxy group, (xi) apolyaryleneoxy group, (xii) a polyarylalkyleneoxy group, (xiii) apolyalkylaryleneoxy group, (xiv) a heterocyclic group, (xv) a silylenegroup, (xvi) a siloxane group, (xvii) a polysilylene group, (xviii) apolysiloxane group, or (xix) hydrogen, provided both R and R′ cannot behydrogen; and

wherein X is a (i) direct bond, (ii) an oxygen atom, (iii) a nitrogenatom, (iv) a sulfur atom, (v) a group of the formula —NR₄₀— wherein R₄₀is a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group,or an alkylaryl group, (vi) or a group of the formula —CR₅₀R₆₀—; whereinR₅₀ and R₆₀ each, independently of the other, is a hydrogen atom, analkyl group, an aryl group, an arylalkyl group, or an alkylaryl group;and

wherein (Y)_(m) and (Z)_(n) are each independently optionally presentand where (Y)_(m) and (Z)_(n) are each independently selected from i) ahydrogen atom, (ii) a halogen atom, (iii) a nitro group, (iv) an alkylgroup, (v) an aryl group, (vi) an arylalkyl group, (vii) an alkylarylgroup, (viii) a group of the formula

wherein R₇₀ is an alkyl group, an aryl group, an arylalkyl group, analkylaryl group, an alkoxy group, an aryloxy group, an arylalkyloxygroup, an alkylaryloxy group, a polyalkyleneoxy group, a polyaryleneoxygroup, a polyarylalkyleneoxy group, a polyalkylaryleneoxy group, aheterocyclic group, a silyl group, a siloxane group, a polysilylenegroup, or a polysiloxane group, (ix) a sulfonyl group of the formula—SO₂R₈₀ wherein R₈₀ is a hydrogen atom, an alkyl group, an aryl group,an arylalkyl group, an alkylaryl group, an alkoxy group, an aryloxygroup, an arylalkyloxy group, an alkylaryloxy group, a polyalkyleneoxygroup, a polyaryleneoxy group, a polyarylalkyleneoxy group, apolyalkylaryleneoxy group, a heterocyclic group, a silyl group, asiloxane group, a polysilylene group, or a polysiloxane group, or (x) aphosphoryl group of the formula —PO₃R₉₀ wherein R₉₀ is a hydrogen atom,an alkyl group, an aryl group, an arylalkyl group, an alkylaryl group,an alkoxy group, an aryloxy group, an arylalkyloxy group, analkylaryloxy group, a polyalkyleneoxy group, a polyaryleneoxy group, apolyarylalkyleneoxy group, a polyalkylaryleneoxy group, a heterocyclicgroup, a silyl group, a siloxane group, a polysilylene group, or apolysiloxane group.

and in (Y)m, m is an integer from about 0 to about 4, or about 1 toabout 3, or about 2 to about 3, and in (Z)n, n is an integer from about0 to about 4, or about 1 to about 3, or about 2 to about 3.

DETAILED DESCRIPTION

The present disclosure is directed to colorant compounds particularlysuitable for use in hot melt or phase change inks. In embodiments, thepresent disclosure is directed to dimeric colorant compoundsparticularly suitable for use in hot melt or phase change inks. Oneembodiment of the present disclosure is directed to compounds of theformula (enol form)

wherein the compound can be dimerized through R or R′, including forexample, in embodiments, compounds of the formula

or a compound of the formula (keto form)

wherein the compound can be dimerized through R or R′, including forexample, in embodiments, compounds of the formula

wherein R and R′ are each independently selected from (i) an alkyl group(including linear, branched, saturated, unsaturated, cyclic,unsubstituted, and substituted alkyl groups, and wherein hetero atoms,such as oxygen, nitrogen, sulfur, silicon, phosphorus, boron, and thelike either may or may not be present in the alkyl group), in oneembodiment with at least about 1 to about carbon atoms, in anotherembodiment with at least about 2 to about 20 carbon atoms, in anotherembodiment with at least about 4 to about 12 carbon atoms, although thenumber of carbon atoms can be outside of these ranges;

(ii) an alkylene group, (including linear, branched, saturated,unsaturated, cyclic, an alkylene group including aliphatic cyclicmoieties therein, unsubstituted, and substituted alkylene groups, andwherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, boron, and the like either may or may not be present in thealkylene group), in one embodiment with at least 1 carbon atom, inanother embodiment with at least about 10 carbon atoms, in yet anotherembodiment with at least about 20 carbon atoms, in still anotherembodiment with at least about 36 carbon atoms, in one embodiment withno more than about 200 carbon atoms, in another embodiment with no morethan about 100 carbon atoms, in another embodiment, with no more thanabout 60 carbon atoms, in yet another embodiment with no more than about40 carbon atoms, although the number of carbon atoms can be outside ofthese ranges;

(iii) an arylene group (including unsubstituted and substituted arylenegroups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, boron, and the like either may or may not bepresent in the arylene group), in one embodiment with at least about 6carbon atoms, in another embodiment with at least about 13 carbon atoms,in still another embodiment with at least about 18 carbon atoms, and inyet another embodiment with at least about 23 carbon atoms, and in oneembodiment with no more than about 100 carbon atoms, in anotherembodiment with no more than about 75 carbon atoms, and in yet anotherembodiment with no more than about 50 carbon atoms, although the numberof carbon atoms can be outside of these ranges;

(iv) an arylalkylene group (including unsubstituted and substitutedarylalkylene groups, and wherein hetero atoms, such as oxygen, nitrogen,sulfur, silicon, phosphorus, boron, and the like either may or may notbe present in either the aryl or the alkyl portion of the arylalkylenegroup), in one embodiment with at least about 7 carbon atoms, in anotherembodiment with at least about 18 carbon atoms, in yet anotherembodiment with at least about 30 carbon atoms, in another embodimentwith at least about 42 carbon atoms, and in one embodiment with no morethan about 200 carbon atoms, in another embodiment with no more thanabout 100 carbon atoms, and in yet another embodiment with no more thanabout 44 carbon atoms, although the number of carbon atoms can beoutside of these ranges;

(v) an alkylarylene group, (including unsubstituted and substitutedalkylarylene groups, and wherein hetero atoms, such as oxygen, nitrogen,sulfur, silicon, phosphorus, boron, and the like either may or may notbe present in either the alkyl or the aryl portion of the alkylarylenegroup), in one embodiment with at least about 7 carbon atoms, in anotherembodiment with at least about 18 carbon atoms, in yet anotherembodiment with at least about 30 carbon atoms, in another embodimentwith at least about 42 carbon atoms, and in one embodiment with no morethan about 200 carbon atoms, in another embodiment with no more thanabout 100 carbon atoms, and in yet another embodiment with no more thanabout 44 carbon atoms, although the number of carbon atoms can beoutside of these ranges;

(vi) an alkyleneoxy group, (including linear, branched, saturated,unsaturated, cyclic, unsubstituted, and substituted alkyleneoxy groups,and wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, boron, and the like either may or may not be present in thealkyl portion of the alkyleneoxy group), in one embodiment with at least1 carbon atom, in another embodiment with at least about 10 carbonatoms, in another embodiment with at least about 20 carbon atoms, and inone embodiment with no more than about 200 carbon atoms, in anotherembodiment with no more than about 100 carbon atoms, in still anotherembodiment with no more than about 60 carbon atoms;

(vii) an aryleneoxy group, (including unsubstituted and substitutedaryleneoxy groups, and wherein hetero atoms, such as oxygen, nitrogen,sulfur, silicon, phosphorus, boron, and the like either may or may notbe present in the aryl portion of the aryleneoxy group), in oneembodiment with at least about 6 carbon atoms, in another embodimentwith at least about 13 carbon atoms, in still another embodiment with atleast about 18 carbon atoms, and in one embodiment with no more thanabout 100 carbon atoms, in another embodiment with no more than about 75carbon atoms, and in yet another embodiment with no more than about 50carbon atoms, although the number of carbon atoms can be outside ofthese ranges;

(viii) an arylalkyleneoxy group, (including unsubstituted andsubstituted arylalkyleneoxy groups, and wherein hetero atoms, such asoxygen, nitrogen, sulfur, silicon, phosphorus, boron, and the likeeither may or may not be present in the either the aryl or the alkylportion of the arylalkyleneoxy group), in one embodiment with at leastabout 7 carbon atoms, in another embodiment with at least about 18carbon atoms, in yet another embodiment with at least about 30 carbonatoms, in another embodiment with at least about 42 carbon atoms, and inone embodiment with no more than about 200 carbon atoms, in anotherembodiment with no more than about 100 carbon atoms, and in yet anotherembodiment with no more than about 44 carbon atoms, although the numberof carbon atoms can be outside of these ranges;

(ix) an alkylaryleneoxy group, (including unsubstituted and substitutedalkylaryleneoxy groups, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, boron, and the like either may ormay not be present in the alkyl or the aryl portion of thealkylaryleneoxy group), in one embodiment with at least about 7 carbonatoms, in another embodiment with at least about 18 carbon atoms, in yetanother embodiment with at least about 30 carbon atoms, in anotherembodiment with at least about 42 carbon atoms, and in one embodimentwith no more than about 200 carbon atoms, in another embodiment with nomore than about 100 carbon atoms, and in yet another embodiment with nomore than about 44 carbon atoms, although the number of carbon atoms canbe outside of these ranges;

(x) a polyalkyleneoxy group, wherein the alkyl portion of the repeatalkyleneoxy groups typically has from about 1 to about 12 carbon atoms,although the number of carbon atoms can be outside of these ranges, suchas a polyethyleneoxy group, a polypropyleneoxy group, a polybutyleneoxygroup, or the like, and wherein the number of repeat alkyleneoxy groupstypically is from about 2 to about 50 repeat alkyleneoxy groups,although the number of repeat units can be outside of these ranges;

(xi) a polyaryleneoxy group, wherein the aryl portion of the repeataryleneoxy groups typically has from about 6 to about 14 carbon atoms,although the number of carbon atoms can be outside of these ranges, suchas a polyphenyleneoxy group, a polynaphthaleneoxy group, apolyphenanthreneoxy group, or the like, and wherein the number of repeataryleneoxy groups typically is from about 2 to about 20 repeataryleneoxy groups, although the number of repeat units can be outside ofthese ranges;

(xii) a polyarylalkyleneoxy group, wherein the arylalkyl portion of therepeat arylalkyleneoxy groups typically has from about 7 to about 50carbon atoms, although the number of carbon atoms can be outside ofthese ranges, such as a polybenzyleneoxy group, a polyphenylethyleneoxygroup, or the like, and wherein the number of repeat arylalkyleneoxygroups typically is from about 2 to about 20 repeat arylalkyleneoxygroups, although the number of repeat units can be outside of theseranges;

(xiii) a polyalkylaryleneoxy group, wherein the alkylaryl portion of therepeat alkylaryleneoxy groups typically has from about 7 to about 50carbon atoms, although the number of carbon atoms can be outside ofthese ranges, such as a polytolueneoxy group or the like, and whereinthe number of repeat alkylaryleneoxy groups typically is from about 2 toabout 20 repeat alkylaryleneoxy groups, although the number of repeatunits can be outside of these ranges;

(xiv) a heterocyclic group, (including unsubstituted and substitutedheterocyclic groups), typically with from about 2 to about 12 carbonatoms, and typically with from about 4 to about 18 ring atoms, althoughthe number of carbon atoms and the number of ring atoms can be outsideof these ranges, wherein the heteroatoms in the heterocyclic groups canbe (but are not limited to) nitrogen, oxygen, sulfur, silicon,phosphorus, boron, and the like, as well as mixtures thereof;

(xv) a silylene group, (including unsubstituted and substituted silylenegroups);

(xvi) a siloxane group, (including unsubstituted and substitutedsiloxane groups);

(xvii) a polysilylene group, (including unsubstituted and substitutedpolysilylene groups), typically with from 2 to about 100 repeat silyleneunits, or

(xviii) a polysiloxane group (including unsubstituted and substitutedpolysiloxane groups), typically with from 2 to about 200 repeat siloxaneunits, although the number of repeat siloxane units can be outside ofthis range, wherein the substituents on the substituted alkylene,arylene, arylalkylene, alkylarylene, alkyleneoxy, aryleneoxy,arylalkyleneoxy, alkylaryleneoxy, polyalkyleneoxy, polyaryleneoxy,polyarylalkyleneoxy, polyalkylaryleneoxy, heterocyclic, silylene,siloxy, polysilylene, and polysiloxy groups are hydroxy groups, halogenatoms, cyano groups, ether groups, aldehyde groups, ketone groups,carboxylic acid groups, ester groups, amide groups, carbonyl groups,thiocarbonyl groups, sulfate groups, sulfonate groups, sulfide groups,sulfoxide groups, phosphate groups, nitrile groups, mercapto groups,nitro groups, nitroso groups, sulfone groups, acyl groups, acidanhydride groups, azide groups, cyanato groups, isocyanato groups,thiocyanato groups, isothiocyanato groups, mixtures thereof, and thelike, wherein the substituents on the silylene, siloxy, polysilylene,and polysiloxy groups can also be alkyl groups, aryl groups, arylalkylgroups, and alkylaryl groups, wherein two or more substituents can bejoined together to form a ring; or

(xix) hydrogen, provided both R and R′ cannot be hydrogen;

wherein X is a (i) direct bond, (ii) an oxygen atom, (iii) a nitrogenatom, (iv) a sulfur atom, (v) a group of the formula —NR₄₀— wherein R₄₀is a hydrogen atom, an alkyl group (including linear, branched,saturated, unsaturated, cyclic, unsubstituted, and substituted alkylgroups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, boron, and the like either may or may not bepresent in the alkyl group), typically with from 1 to about 50 carbonatoms, or from about 2 to about 20 carbon atoms, or from about 4 toabout 12 carbon atoms, although the number of carbon atoms can beoutside of these ranges, an aryl group (including substituted arylgroups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, boron, and the like either may or may not bepresent in the aryl group), typically with from about 6 to about 50carbon atoms, or from about 6 to about 20 carbon atoms, or from about 6to about 10 carbon atoms, although the number of carbon atoms can beoutside of these ranges, an arylalkyl group (including substitutedarylalkyl groups, and wherein hetero atoms, such as oxygen, nitrogen,sulfur, silicon, phosphorus, boron, and the like either may or may notbe present in either the aryl portion or the alkyl portion of thearylalkyl group), typically with from about 7 to about 100 carbon atoms,or from about 7 to about 50 carbon atoms, or from about 7 to about 20carbon atoms, although the number of carbon atoms can be outside ofthese ranges, or an alkylaryl group (including substituted alkylarylgroups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, boron, and the like either may or may not bepresent in the alkyl portion or the aryl portion of the alkylarylgroup), typically with from about 7 to about 100 carbon atoms, or fromabout 7 to about 50 carbon atoms, or from about 7 to about 20 carbonatoms, although the number of carbon atoms can be outside of theseranges, or (v) a group of the formula —CR₅₀R₆₀— wherein R₅₀ and R₆₀each, independently of the other, is a hydrogen atom, an alkyl group(including linear, branched, saturated, unsaturated, cyclic,unsubstituted, and substituted alkyl groups, and wherein hetero atoms,such as oxygen, nitrogen, sulfur, silicon, phosphorus, boron, and thelike either may or may not be present in the alkyl group), typicallywith from 1 to about 50 carbon atoms, or from about 2 to about 20 carbonatoms, or from about 4 to about 12 carbon atoms, although the number ofcarbon atoms can be outside of these ranges, an aryl group (includingsubstituted aryl groups, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, boron, and the like either may ormay not be present in the aryl group), typically with from about 6 toabout 50 carbon atoms, or from about 6 to about 20 carbon atoms, or fromabout 6 to about 10 carbon atoms, although the number of carbon atomscan be outside of these ranges, an arylalkyl group (includingsubstituted arylalkyl groups, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, boron, and the like either may ormay not be present in the aryl portion or the alkyl portion of thearylalkyl group), typically with from about 7 to about 100 carbon atoms,or from about 7 to about 50 carbon atoms, or from about 7 to about 20carbon atoms, although the number of carbon atoms can be outside ofthese ranges, or an alkylaryl group (including substituted alkylarylgroups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, boron, and the like either may or may not bepresent in the alkyl portion or the aryl portion of the alkylarylgroup), typically with from about 7 to about 100 carbon atoms, or fromabout 7 to about 50 carbon atoms, or from about 7 to about 20 carbonatoms, although the number of carbon atoms can be outside of theseranges, wherein the substituents on the substituted alkyl, aryl,arylalkyl, and alkylaryl groups can be (but are not limited to) hydroxygroups, halogen atoms, amine groups, imine groups, ammonium groups,pyridine groups, pyridinium groups, ether groups, aldehyde groups, estergroups, amide groups, carbonyl groups, thiocarbonyl groups, sulfategroups, sulfonate groups, sulfide groups, sulfoxide groups, phosphinegroups, phosphonium groups, phosphate groups, nitrile groups, mercaptogroups, nitro groups, nitroso groups, sulfone groups, acyl groups, acidanhydride groups, azide groups, cyanato groups, isocyanato groups,thiocyanato groups, isothiocyanato groups, mixtures thereof, and thelike, wherein two or more substituents can be joined together to form aring; and

(Y)_(m) and (Z)_(n) each, independently of the others, is (i) a hydrogenatom, (ii) a halogen atom, including fluorine, chlorine, bromine, andiodine, (iii) a nitro group, (iv) an alkyl group (including linear,branched, saturated, unsaturated, cyclic, unsubstituted, and substitutedalkyl groups, and wherein hetero atoms, such as oxygen, nitrogen,sulfur, silicon, phosphorus, boron, and the like either may or may notbe present in the alkyl group), typically with from 1 to about 50 carbonatoms, or from about 1 to about 20 carbon atoms, and or from about 1 toabout 10 carbon atoms, although the number of carbon atoms can beoutside of these ranges, (v) an aryl group (including substituted arylgroups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, boron, and the like either may or may not bepresent in the aryl group), typically with from about 6 to about 50carbon atoms, or from about 6 to about 14 carbon atoms, or from about 6to about 10 carbon atoms, although the number of carbon atoms can beoutside of these ranges, (vi) an arylalkyl group (including substitutedarylalkyl groups, and wherein hetero atoms, such as oxygen, nitrogen,sulfur, silicon, phosphorus, boron, and the like either may or may notbe present in either the aryl portion or the alkyl portion of thearylalkyl group), typically with from about 7 to about 50 carbon atoms,or from about 7 to about 25 carbon atoms, and or from about 7 to about15 carbon atoms, although the number of carbon atoms can be outside ofthese ranges, (vii) an alkylaryl group (including substituted alkylarylgroups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, boron, and the like either may or may not bepresent in the alkyl portion or the aryl portion of the alkylarylgroup), typically with from about 7 to about 50 carbon atoms, or fromabout 7 to about 25 carbon atoms, or from about 7 to about 15 carbonatoms, although the number of carbon atoms can be outside of theseranges, (viii) a group of the formula

wherein R₇₀ is an alkyl group (including linear, branched, saturated,unsaturated, cyclic, unsubstituted, and substituted alkyl groups, andwherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, boron, and the like either may or may not be present in thealkyl group), typically with from 1 to about 50 carbon atoms, or fromabout 1 to about 20 carbon atoms, or from about 1 to about 10 carbonatoms, although the number of carbon atoms can be outside of theseranges, an aryl group (including substituted aryl groups, and whereinhetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus,boron, and the like either may or may not be present in the aryl group),typically with from about 6 to about 50 carbon atoms, or about 6 toabout 20 carbon atoms, or about 6 to about 14 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, an arylalkylgroup (including substituted arylalkyl groups, and wherein hetero atoms,such as oxygen, nitrogen, sulfur, silicon, phosphorus, boron, and thelike either may or may not be present in the aryl portion or the alkylportion of the arylalkyl group), typically with from about 7 to about 50carbon atoms, or about 7 to about 25 carbon atoms, and or about 7 toabout 15 carbon atoms, although the number of carbon atoms can beoutside of these ranges, an alkylaryl group (including substitutedalkylaryl groups, and wherein hetero atoms, such as oxygen, nitrogen,sulfur, silicon, phosphorus, boron, and the like either may or may notbe present in the alkyl portion or the aryl portion of the alkylarylgroup), typically with from about 7 to about 50 carbon atoms, or about 7to about 25 carbon atoms, or about 7 to about 15 carbon atoms, althoughthe number of carbon atoms can be outside of these ranges, an alkoxygroup (including linear, branched, saturated, unsaturated, cyclic,unsubstituted, and substituted alkoxy groups, and wherein hetero atoms,such as oxygen, nitrogen, sulfur, silicon, phosphorus, boron, and thelike either may or may not be present in the alkyl portion of the alkoxygroup), typically with from about 1 to about 50 carbon atoms, or about 4to about 20 carbon atoms, or about 8 to about 12 carbon atoms, althoughthe number of carbon atoms can be outside of these ranges, an aryloxygroup (including substituted aryloxy groups, and wherein hetero atoms,such as oxygen, nitrogen, sulfur, silicon, phosphorus, boron, and thelike either may or may not be present in the aryl portion of the aryloxygroup), typically with from about 6 to about 50 carbon atoms, or about 6to about 20 carbon atoms, or about 6 to about 14 carbon atoms, althoughthe number of carbon atoms can be outside of these ranges, anarylalkyloxy group (including substituted arylalkyloxy groups, andwherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, boron, and the like either may or may not be present in thearyl portion or the alkyl portion of the arylalkyloxy group), typicallywith from about 7 to about 50 carbon atoms, or about 7 to about 25carbon atoms, or about 7 to about 15 carbon atoms, although the numberof carbon atoms can be outside of these ranges, an alkylaryloxy group(including substituted alkylaryloxy groups, and wherein hetero atoms,such as oxygen, nitrogen, sulfur, silicon, phosphorus, boron, and thelike either may or may not be present in the alkyl portion or the arylportion of the of the alkylaryloxy group), typically with from about 7to about 50 carbon atoms, or about 7 to about 25 carbon atoms, or about7 to about 15 carbon atoms, although the number of carbon atoms can beoutside of these ranges, a polyalkyleneoxy group, wherein the alkylportion of the repeat alkyleneoxy groups typically has from about 1 toabout 12 carbon atoms, although the number of carbon atoms can beoutside of these ranges, such as a polyethyleneoxy group, apolypropyleneoxy group, a polybutyleneoxy group, or the like, andwherein the number of repeat alkyleneoxy groups typically is from about2 to about 50 repeat alkyleneoxy groups, although the number of repeatunits can be outside of these ranges, a polyaryleneoxy group, whereinthe aryl portion of the repeat aryleneoxy groups typically has fromabout 6 to about 14 carbon atoms, although the number of carbon atomscan be outside of these ranges, such as a polyphenyleneoxy group, apolynaphthaleneoxy group, a polyphenanthreneoxy group, or the like, andwherein the number of repeat aryleneoxy groups typically is from about 2to about 20 repeat aryleneoxy groups, although the number of repeatunits can be outside of these ranges, a polyarylalkyleneoxy group,wherein the arylalkyl portion of the repeat arylalkyleneoxy groupstypically has from about 7 to about 50 carbon atoms, although the numberof carbon atoms can be outside of these ranges, such as apolybenzyleneoxy group, a polyphenylethyleneoxy group, or the like, andwherein the number of repeat arylalkyleneoxy groups typically is fromabout 2 to about 20 repeat arylalkyleneoxy groups, although the numberof repeat units can be outside of these ranges, a polyalkylaryleneoxygroup, wherein the alkylaryl portion of the repeat alkylaryleneoxygroups typically has from about 7 to about 50 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, such as apolytolueneoxy group or the like, and wherein the number of repeatalkylaryleneoxy groups typically is from about 2 to about 20 repeatalkylaryleneoxy groups, although the number of repeat units can beoutside of these ranges, a heterocyclic group (including unsubstitutedand substituted heterocyclic groups), typically with from about 2 toabout 12 carbon atoms, and typically with from about 4 to about 18 ringatoms, although the number of carbon atoms and the number of ring atomscan be outside of these ranges, wherein the heteroatoms in theheterocyclic groups can be (but are not limited to) nitrogen, oxygen,sulfur, silicon, phosphorus, boron, and the like, as well as mixturesthereof, a silyl group (including unsubstituted and substituted silylgroups), a siloxane group (including unsubstituted and substitutedsiloxane groups), a polysilylene group (including unsubstituted andsubstituted polysilylene groups), typically with from 2 to about 100repeat silylene units, or a polysiloxane group (including unsubstitutedand substituted polysiloxane groups), typically with from 2 to about 200repeat siloxane units, although the number of repeat siloxane units canbe outside of this range, (ix) a sulfonyl group of the formula —SO₂R₈₀,wherein R₈₀ is a hydrogen atom, an alkyl group (including linear,branched, saturated, unsaturated, cyclic, unsubstituted, and substitutedalkyl groups, and wherein hetero atoms, such as oxygen, nitrogen,sulfur, silicon, phosphorus, boron, and the like either may or may notbe present in the alkyl group), typically with from 1 to about 50 carbonatoms, or about 1 to about 20 carbon atoms, or about 1 to about 10carbon atoms, although the number of carbon atoms can be outside ofthese ranges, an aryl group (including substituted aryl groups, andwherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, boron, and the like either may or may not be present in thearyl group), typically with from about 6 to about 50 carbon atoms, orabout 6 to about 20 carbon atoms, or about 6 to about 14 carbon atoms,although the number of carbon atoms can be outside of these ranges, anarylalkyl group (including substituted arylalkyl groups, and whereinhetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus,boron, and the like either may or may not be present in the aryl portionor the alkyl portion of the arylalkyl group), typically with from about7 to about 50 carbon atoms, or about 7 to about 25 carbon atoms, orabout 7 to about 15 carbon atoms, although the number of carbon atomscan be outside of these ranges, an alkylaryl group (includingsubstituted alkylaryl groups, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, boron, and the like either may ormay not be present in the alkyl portion or the aryl portion of thealkylaryl group), typically with from about 7 to about 50 carbon atoms,or about 7 to about 25 carbon atoms, or about 7 to about 15 carbonatoms, although the number of carbon atoms can be outside of theseranges, an alkoxy group (including linear, branched, saturated,unsaturated, cyclic, unsubstituted, and substituted alkoxy groups, andwherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, boron, and the like either may or may not be present in thealkyl portion of the alkoxy group), typically with from about 1 to about50 carbon atoms, or about 4 to about 20 carbon atoms, or about 8 toabout 12 carbon atoms, although the number of carbon atoms can beoutside of these ranges, an aryloxy group (including substituted aryloxygroups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, boron, and the like either may or may not bepresent in the aryl portion of the aryloxy group), typically with fromabout 6 to about 50 carbon atoms, or about 6 to about 20 carbon atoms,or about 6 to about 14 carbon atoms, although the number of carbon atomscan be outside of these ranges, an arylalkyloxy group (includingsubstituted arylalkyloxy groups, and wherein hetero atoms, such asoxygen, nitrogen, sulfur, silicon, phosphorus, boron, and the likeeither may or may not be present in the aryl portion or the alkylportion of the arylalkyloxy group), typically with from about 7 to about50 carbon atoms, or about 7 to about 25 carbon atoms, or about 7 toabout 15 carbon atoms, although the number of carbon atoms can beoutside of these ranges, an alkylaryloxy group (including substitutedalkylaryloxy groups, and wherein hetero atoms, such as oxygen, nitrogen,sulfur, silicon, phosphorus, boron, and the like either may or may notbe present in the alkyl portion or the aryl portion of the alkylaryloxygroup), typically with from about 7 to about 50 carbon atoms, or about 7to about 25 carbon atoms, or about 7 to about 15 carbon atoms, althoughthe number of carbon atoms can be outside of these ranges, apolyalkyleneoxy group, wherein the alkyl portion of the repeatalkyleneoxy groups typically has from about 1 to about 12 carbon atoms,although the number of carbon atoms can be outside of these ranges, suchas a polyethyleneoxy group, a polypropyleneoxy group, a polybutyleneoxygroup, or the like, and wherein the number of repeat alkyleneoxy groupstypically is from about 2 to about 50 repeat alkyleneoxy groups,although the number of repeat units can be outside of these ranges, apolyaryleneoxy group, wherein the aryl portion of the repeat aryleneoxygroups typically has from about 6 to about 14 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, such as apolyphenyleneoxy group, a polynaphthaleneoxy group, apolyphenanthreneoxy group, or the like, and wherein the number of repeataryleneoxy groups typically is from about 2 to about 20 repeataryleneoxy groups, although the number of repeat units can be outside ofthese ranges, a polyarylalkyleneoxy group, wherein the arylalkyl portionof the repeat arylalkyleneoxy groups typically has from about 7 to about50 carbon atoms, although the number of carbon atoms can be outside ofthese ranges, such as a polybenzyleneoxy group, a polyphenylethyleneoxygroup, or the like, and wherein the number of repeat arylalkyleneoxygroups typically is from about 2 to about 20 repeat arylalkyleneoxygroups, although the number of repeat units can be outside of theseranges, a polyalkylaryleneoxy group, wherein the alkylaryl portion ofthe repeat alkylaryleneoxy groups typically has from about 7 to about 50carbon atoms, although the number of carbon atoms can be outside ofthese ranges, such as a polytolueneoxy group or the like, and whereinthe number of repeat alkylaryleneoxy groups typically is from about 2 toabout 20 repeat alkylaryleneoxy groups, although the number of repeatunits can be outside of these ranges, a heterocyclic group (includingunsubstituted and substituted heterocyclic groups), typically with fromabout 2 to about 12 carbon atoms, and typically with from about 4 toabout 18 ring atoms, although the number of carbon atoms and the numberof ring atoms can be outside of these ranges, wherein the heteroatoms inthe heterocyclic groups can be (but are not limited to) nitrogen,oxygen, sulfur, silicon, phosphorus, boron, and the like, as well asmixtures thereof, a silyl group (including unsubstituted and substitutedsilyl groups), a siloxane group (including unsubstituted and substitutedsiloxane groups), a polysilylene group (including unsubstituted andsubstituted polysilylene groups), typically with from 2 to about 100repeat silylene units, or a polysiloxane group (including unsubstitutedand substituted polysiloxane groups), typically with from 2 to about 200repeat siloxane units, although the number of repeat siloxane units canbe outside of this range, or (x) a phosphoryl group of the formula—PO₃R₉₀, wherein R₉₀ is a hydrogen atom, an alkyl group (includinglinear, branched, saturated, unsaturated, cyclic, unsubstituted, andsubstituted alkyl groups, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, boron, and the like either may ormay not be present in the alkyl group), typically with from 1 to about50 carbon atoms, or about 1 to about 20 carbon atoms, or about 1 toabout 10 carbon atoms, although the number of carbon atoms can beoutside of these ranges, an aryl group (including substituted arylgroups), typically with from about 6 to about 50 carbon atoms, or about6 to about 20 carbon atoms, or about 6 to about 14 carbon atoms,although the number of carbon atoms can be outside of these ranges, anarylalkyl group (including substituted arylalkyl groups), typically withfrom about 7 to about 50 carbon atoms, or about 7 to about 25 carbonatoms, or about 7 to about 15 carbon atoms, although the number ofcarbon atoms can be outside of these ranges, an alkylaryl group(including substituted alkylaryl groups), typically with from about 7 toabout 50 carbon atoms, or about 7 to about 25 carbon atoms, or about 7to about 15 carbon atoms, although the number of carbon atoms can beoutside of these ranges, an alkoxy group (including linear, branched,saturated, unsaturated, cyclic, unsubstituted, and substituted alkoxygroups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, boron, and the like either may or may not bepresent in the alkyl portion of the alkoxy group), typically with fromabout 1 to about 50 carbon atoms, or about 4 to about 20 carbon atoms,or about 8 to about 12 carbon atoms, although the number of carbon atomscan be outside of these ranges, an aryloxy group (including substitutedaryloxy groups), typically with from about 6 to about 50 carbon atoms,preferably with from about 6 to about 20 carbon atoms, or about 6 toabout 14 carbon atoms, although the number of carbon atoms can beoutside of these ranges, an arylalkyloxy group (including substitutedarylalkyloxy groups), typically with from about 7 to about 50 carbonatoms, or about 7 to about 25 carbon atoms, or about 7 to about 15carbon atoms, although the number of carbon atoms can be outside ofthese ranges, an alkylaryloxy group (including substituted alkylaryloxygroups), typically with from about 7 to about 50 carbon atoms, or about7 to about 25 carbon atoms, or about 7 to about 15 carbon atoms,although the number of carbon atoms can be outside of these ranges, apolyalkyleneoxy group, wherein the alkyl portion of the repeatalkyleneoxy groups typically has from about 1 to about 12 carbon atoms,although the number of carbon atoms can be outside of these ranges, suchas a polyethyleneoxy group, a polypropyleneoxy group, a polybutyleneoxygroup, or the like, and wherein the number of repeat alkyleneoxy groupstypically is from about 2 to about 50 repeat alkyleneoxy groups,although the number of repeat units can be outside of these ranges, apolyaryleneoxy group, wherein the aryl portion of the repeat aryleneoxygroups typically has from about 6 to about 14 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, such as apolyphenyleneoxy group, a polynaphthaleneoxy group, apolyphenanthreneoxy group, or the like, and wherein the number of repeataryleneoxy groups typically is from about 2 to about 20 repeataryleneoxy groups, although the number of repeat units can be outside ofthese ranges, a polyarylalkyleneoxy group, wherein the arylalkyl portionof the repeat arylalkyleneoxy groups typically has from about 7 to about50 carbon atoms, although the number of carbon atoms can be outside ofthese ranges, such as a polybenzyleneoxy group, a polyphenylethyleneoxygroup, or the like, and wherein the number of repeat arylalkyleneoxygroups typically is from about 2 to about 20 repeat arylalkyleneoxygroups, although the number of repeat units can be outside of theseranges, a polyalkylaryleneoxy group, wherein the alkylaryl portion ofthe repeat alkylaryleneoxy groups typically has from about 7 to about 50carbon atoms, although the number of carbon atoms can be outside ofthese ranges, such as a polytolueneoxy group or the like, and whereinthe number of repeat alkylaryleneoxy groups typically is from about 2 toabout 20 repeat alkylaryleneoxy groups, although the number of repeatunits can be outside of these ranges, a heterocyclic group (includingunsubstituted and substituted heterocyclic groups), typically with fromabout 2 to about 12 carbon atoms, and typically with from about 4 toabout 18 ring atoms, although the number of carbon atoms and the numberof ring atoms can be outside of these ranges, wherein the heteroatoms inthe heterocyclic groups can be (but are not limited to) nitrogen,oxygen, sulfur, silicon, phosphorus, boron, and the like, as well asmixtures thereof, a silyl group (including unsubstituted and substitutedsilyl groups), a siloxane group (including unsubstituted and substitutedsiloxane groups), a polysilylene group (including unsubstituted andsubstituted polysilylene groups), typically with from 2 to about 100repeat silylene units, or a polysiloxane group (including unsubstitutedand substituted polysiloxane groups), typically with from 2 to about 200repeat siloxane units, although the number of repeat siloxane units canbe outside of this range, wherein the substituents on the substitutedalkyl, aryl, arylalkyl, alkylaryl, alkoxy, aryloxy, arylalkyloxy,alkylaryloxy, polyalkyleneoxy, polyaryleneoxy, polyarylalkyleneoxy,polyalkylaryleneoxy, heterocyclic, silyl, siloxy, polysilylene, andpolysiloxy groups are hydroxy groups, halogen atoms, cyano groups, ethergroups, aldehyde groups, ketone groups, carboxylic acid groups, estergroups, amide groups, carbonyl groups, thiocarbonyl groups, sulfategroups, sulfonate groups, sulfide groups, sulfoxide groups, phosphategroups, nitrile groups, mercapto groups, nitro groups, nitroso groups,sulfone groups, acyl groups, acid anhydride groups, azide groups,cyanato groups, isocyanato groups, thiocyanato groups, isothiocyanatogroups, mixtures thereof, and the like, wherein the substituents on thesilylene, siloxy, polysilylene, and polysiloxy groups can also be alkylgroups, aryl groups, arylalkyl groups, and alkylaryl groups, wherein twoor more substituents can be joined together to form a ring, and wherein(Y)_(m) and (Z)_(n) can be the same as each other or different from eachother. Up to 4 (Y)_(m) groups can be present on the molecule. Up to 4(Z)_(n) groups can be present on the molecule.

In (Y)m, m is an integer from about 0 to about 4, or about 1 to about 3,or about 2 to about 3, and in (Z)n, n is an integer from about 0 toabout 4, or about 1 to about 3, or about 2 to about 3.

The group or groups (Y)_(m) can be joined together with R to form anring; and the group or groups (Z)_(n) can be joined together with R′ toform a ring.

Some specific examples of suitable R or R′ groups include (but are notlimited to) the following, wherein one or both R or R′ can be selectedfrom a menthyl group of the formula

n-hexanediyl, of the formula —(CH₂)₆—, n-octanediyl, of the formula—(CH₂)₈—, n-decanediyl, of the formula —(CH₂)₁₀—, n-dodecanediyl, of theformula —(CH₂)₁₂—, 3-methyl-1,5-pentanediyl, of the formula

1,4-cyclohexanedimethylene, of the formula (which is not intended to belimited to any particular stereochemistry and includes all cis and transisomers)

4,4′-isopropylidenedicyclohexanediyl, of the formula (which is notintended to be limited to any particular stereochemistry and includesall cis and trans isomers)

4,4′-bicyclohexyanediyl, of the formula (which is not intended to belimited to any particular stereochemistry and includes all cis and transisomers)

a branched alkylene group having 36 carbon atoms, including isomers ofthe formula

a branched alkylene group having 36 carbon atoms, including isomers ofthe formula

and other branched alkylene isomers (which may include unsaturations andcyclic groups), 4,8-bis(methylene)tricyclo[5210^(2,6)]decanediyl, of theformula (which is not intended to be limited to any particularstereochemistry and includes all cis and trans isomers)

and the like.

Colorants of the present disclosure can be prepared by any desired oreffective procedure. For example, they can be prepared by diazotizationof the correspondingly substituted dimeric anthranilate compound withnitrosylsulfuric acid under cold temperature conditions, followed bycoupling with the correspondingly substituted acetoacetamido in abuffered alkaline aqueous solution under cold temperature conditions, asfollows:

Other methods can be employed including use of KNO₂ or NaNO₂ and amineral acid such as HCl or H₂SO₄. More specifically, thecorrespondingly substituted dianthranilate is first subjected to adiazotization reaction by dissolving it in acetic acid diluted with asolvent and, optionally, a second acid, such as sulfuric acid,dodecylbenzene sulfonic acid, propionic acid, hydrochloric acid,phosphoric acid, any other acid useful for a diazotization reaction, orthe like, as well as mixtures thereof. The solvent can be any solventuseful in a diazotization reaction, such as water, acetone,dimethylformamide, dimethyacetamide, tetrahydrofuran, dimethoxyethane,analogous higher-boiling ether solvents, and the like, as well asmixtures thereof.

The solvent and the dianthranilate are present in any desired oreffective relative amounts; if, for purposes of determining relativeamounts, “solvent” is defined to include whatever solvent has beenselected plus any amount of acetic acid and second acid present, thereactants are present in this combined solvent in relative amounts of inone embodiment at least about 100 grams of substituted dianthranilateper liter of solvent, in another embodiment at least about 200 grams ofsubstituted dianthranilate per liter of solvent, and in yet anotherembodiment at least about 230 grams of substituted dianthranilate perliter of solvent, and in one embodiment of no more than about 400 gramsof substituted dianthranilate per liter of solvent, in anotherembodiment of no more than about 300 grams of substituted dianthranilateper liter of solvent, and in yet another embodiment of no more thanabout 270 grams of substituted dianthranilate per liter of solvent,although the relative amounts can be outside of these ranges.

The acetic acid is present in any desired or effective amount, in oneembodiment at least about 1 gram of acetic acid per gram of substituteddianthranilate, in another embodiment at least about 2 grams of aceticacid per gram of substituted dianthranilate, and in yet anotherembodiment at least about 3 grams of acetic acid per gram of substituteddianthranilate, and in one embodiment no more than about 10 grams ofacetic acid per gram of substituted dianthranilate, in anotherembodiment no more than about 7 grams of acetic acid per gram ofsubstituted dianthranilate, and in yet another embodiment no more thanabout 5 grams of acetic acid per gram of substituted dianthranilate,although the relative amounts can be outside of these ranges.

When present, the optional second acid is present in any desired oreffective amount, in one embodiment at least about 0.05 gram of acid pergram of substituted dianthranilate, and in another embodiment at leastabout 0.1 gram of acid per gram of substituted dianthranilate, and inone embodiment no more than about 0.5 grams of acid per gram ofsubstituted dianthranilate, in another embodiment no more than about 0.3grams of acid per gram of substituted dianthranilate, and in yet anotherembodiment no more than about 0.2 grams of acid per gram of substituteddianthranilate, although the relative amounts can be outside of theseranges.

In the mixture comprising the selected solvent, any optional secondacid, and acetic acid, the acetic acid is present in any desired oreffective amount, in one embodiment at least about 50 percent by volumeof the mixture, in another embodiment at least about 70 percent byvolume of the mixture, in yet another embodiment at least about 75percent by volume of the mixture, and in still another embodiment atleast about 95 percent by volume of the mixture, although the relativeamount can be outside of these ranges.

Upon complete dissolution of the ingredients, the mixture is cooled, inone embodiment to a temperature of no more than about +15° C., inanother embodiment to a temperature of no more than about +10° C., inyet another embodiment to a temperature of no more than about +5° C., instill another embodiment to a temperature of no more than about +3° C.,and in one embodiment to a temperature of no lower than about −5° C.,and in another embodiment to a temperature of no lower than about −10°C., although the temperature can be outside of these ranges.

Thereafter, nitrosylsulfuric acid is added to the mixture in any desiredor effective amount, in one embodiment at least about 2 moles ofnitrosylsulfuric acid per mole of substituted dianthranilate (i.e., atleast about 1 mole of nitrosylsulfuric acid per mole of aniline moietyin the dianthranilate), and in another embodiment at least about 2.1moles of nitrosylsulfuric acid per mole of substituted dianthranilate,and in one embodiment no more than about 3 moles of nitrosylsulfuricacid per mole of substituted dianthranilate, in another embodiment nomore than about 2.5 moles of nitrosylsulfuric acid per mole ofsubstituted dianthranilate, and in yet another embodiment no more thanabout 2.25 moles of nitrosylsulfuric acid per mole of substituteddianthranilate, although the relative amounts can be outside of theseranges. In a specific embodiment, the nitrosylsulfuric acid is addeddropwise at a rate such that the temperature of the reaction mixturedoes not exceed 15° C.

The reaction to form the diazonium salt is essentially instantaneous,and upon completion of addition of the nitrosylsulfuric acid thereaction is essentially complete. At times, the reaction can take aperiod of time to complete, from instantaneous to about 6 hours. Ifdesired, a qualitative test can be performed to confirm reactioncompletion.

Thereafter, residual excess nitrosylsulfuric acid present in thereaction mixture can be quenched by the addition of a quenching agent,such as sulfamic acid, urea, or the like as well as mixtures thereof, inany desired or effective amount, in one embodiment at least about 0.01mole of quenching agent per mole of nitrosylsulfuric acid (i.e., permole of nitrosylsulfuric acid originally added to the reaction mixture),in another embodiment at least about 0.05 mole of quenching agent permole of nitrosylsulfuric acid, and in yet another embodiment at leastabout 0.1 mole of quenching agent per mole of nitrosylsulfuric acid, andin one embodiment no more than about 0.5 mole of quenching agent permole of nitrosylsulfuric acid, in another embodiment no more than about0.3 mole of quenching agent per mole of nitrosylsulfuric acid, and inyet another embodiment no more than about 0.2 mole of quenching agentper mole of nitrosylsulfuric acid, although the amount can be outside ofthese ranges. Upon completion of the reaction, the reaction mixturecontains the corresponding diazonium salt.

A precursor solution of the pyrazolone having the desired substituentsthereon is prepared in an appropriate solvent, such as a mixture ofwater, organic solvents, including lower alcohols such as methanol,ethanol, isopropanol, and the like, water-miscible nonbasic organicsolvents such as tetrahydrofuran, acetone, dimethoxyethane,N,N-dimethylformamide, N,N-dimethylacetamide, acetonitrile, sodiumacetate/acetic acid, and the like, as well as mixtures thereof. Mixturesof water with an organic solvent can be helpful for ease of solvatinginorganic or organic salts that are a reaction by-product. In thisinstance, water and the organic solvent are present in any desired oreffective relative amounts, in one embodiment at least about 0.25 gramof organic solvent per gram of water, in another embodiment at leastabout 0.3 gram of organic solvent per gram of water, and in yet anotherembodiment at least about 0.4 gram of organic solvent per gram of water,and in one embodiment no more than about 4 grams of organic solvent pergram of water, in another embodiment no more than about 3 grams oforganic solvent per gram of water, and in yet another embodiment no morethan about 2 grams of organic solvent per gram of water, although therelative amounts can be outside of these ranges.

The pyrazolone is present in the precursor solution in any desired oreffective amount, in one embodiment at least about 10 grams ofpyrazolone per liter of solvent, in another embodiment at least about 30grams of pyrazolone per liter of solvent, and in yet another embodimentat least about 50 grams of pyrazolone per liter of solvent, and in oneembodiment no more than about 200 grams of pyrazolone per liter ofsolvent, in another embodiment no more than about 100 grams ofpyrazolone per liter of solvent, and in yet another embodiment no morethan about 70 grams of pyrazolone per liter of solvent, although therelative amounts can be outside of these ranges.

The pyrazolone precursor solution is maintained at an alkaline pH,typically of at least about 10, and in one embodiment no more than about14, and in another embodiment no more than about 12, although the pH canbe outside of these ranges. The pyrazolone precursor solution cancontain a mixture of a base and an optional buffering salt.

Examples of suitable bases include mineral bases, such as sodiumhydroxide, potassium hydroxide, and the like, as well as water-miscibleorganic tertiary amines, such as triethanolamine,N,N-diethylethanolamine, and the like, as well as mixtures thereof,present in any desired or effective amount, in one embodiment at leastabout 1 mole of base per mole of pyrazolone, in another embodiment atleast about 2 moles of base per mole of pyrazolone, in yet anotherembodiment at least about 3 moles of base per mole of pyrazolone, and instill another embodiment at least about 5 moles of base per mole ofpyrazolone, and in one embodiment no more than about 10 moles of baseper mole of pyrazolone, in another embodiment no more than about 7 molesof base per mole of pyrazolone, and in yet another embodiment no morethan about 5 moles of base per mole of pyrazolone, although the relativeamounts can be outside of these ranges.

Examples of suitable optional buffer salts include those correspondingto the principal acid solvent; for example, when the principal acidsolvent is acetic acid, suitable buffers include sodium acetate,potassium acetate, sodium hydrogenphosphate, citric acid, and the like,as well as mixtures thereof. When present, the optional buffer salt ispresent in any desired or effective amount, in one embodiment at leastabout 1 mole of buffer per mole of a pyrazolone, in another embodimentat least about 2 moles of buffer per mole of pyrazolone, in yet anotherembodiment at least about 3 moles of buffer per mole of pyrazolone, andin still another embodiment at least about 5 moles of buffer per mole ofpyrazolone, and in one embodiment no more than about 10 moles of bufferper mole of pyrazolone, in another embodiment no more than about 7 molesof buffer per mole of pyrazolone, and in yet another embodiment no morethan about 5 moles of buffer per mole of pyrazolone, although therelative amounts can be outside of these ranges. In a specificembodiment, upon dissolution of the pyrazolone, the thus-formedprecursor pyrazolone solution can be filtered to remove any undissolvedsolids.

The solution containing the diazonium salt, maintained at a coldtemperature, is then slowly added to the pyrazolone solution in anydesired or effective relative amounts. If the diazonium salt is of adimeric species (that is, a bis-diazonium salt), in one embodiment atleast about 2 moles of acetoacetamide per mole of diazonium salt, inanother embodiment at least about 2.1 moles of acetoacetamide per moleof diazonium salt, and in yet another embodiment at least about 2.25moles of acetoacetamide per mole of diazonium salt, and in oneembodiment no more than about 4 moles of acetoacetamide per mole ofdiazonium salt, in another embodiment no more than about 3 moles ofacetoacetamide per mole of diazonium salt, and in yet another embodimentno more than about 2.5 moles of acetoacetamide per mole of diazoniumsalt, if a monomeric diazonium salt is selected, the moles ofacetoacetamide should be halved, although the relative amounts can beoutside of these ranges, resulting in the immediate formation of abright yellow precipitate. Thereafter, the yellow precipitate can becollected by filtration and, if desired, washed.

Precursor dianthranilates can be prepared by any desired or effectivemethod, such as that disclosed in, for example, U.S. Pat. No. 6,713,614and U.S. Pat. No. 6,576,747; the disclosures of each of which aretotally incorporated herein by reference.

Precursor pyrazolones can be prepared by any desired or effectivemethod, such as that disclosed in, for example, Advanced OrganicChemistry: Reactions, Mechanisms and Structures, Jerry March, SecondEdition, 1977, page 825, McGraw Hill, Inc., the disclosure of which istotally incorporated herein by reference.

Embodiments of the present colorants include, for example, but are notlimited to, a compound of the formula

In another embodiment, colorants herein include, for example, a compoundof the formula

In yet another embodiment, colorants herein include a compound of theformula

In yet another embodiment, colorants herein include a compound of theformula

While not being limited to any particular theory, it is believed that inembodiments the structure of the present compounds provide improvedmigratory and diffusion properties. Further, while not being limited toany particular theory, it is believed that in embodiments the waxyappendages (that is, long chains) protruding from the chromophore ateach end provide a compound that is compatible and soluble in the phasechange ink base. It is believed that this structural feature can alsoimpart thermal stability and chemical stability to the colorantmolecule. Further, while not being limited to any particular theory, itis believed that including alkyl or alkylene groups with at least about12 carbon atoms, particularly (although not necessarily) branched alkylgroups of this type, in the colorant molecule further reduce diffusionor leaching of the colorant molecule from a medium such as a phasechange ink vehicle into adjacent inks of different colors (leading tointercolor bleed), adjacent unprinted areas (leading to edgeraggedness), tape adhesives (leading to edge raggedness and possibleillegibility), and the like.

In addition to being suitable for use in phase change inks, thecolorants of the present invention can be used in applications such astextile dying, biological dying applications that rely on high spectralstrength chromophores, electronics applications, such as organicphotoconductors, optical filters, and the like, color filters for liquidcrystal display systems, and the like.

EXAMPLES

The following Examples are being submitted to further define variousspecies of the present disclosure. These Examples are intended to beillustrative only and are not intended to limit the scope of the presentdisclosure. Also, parts and percentages are by weight unless otherwiseindicated.

Example 1 Dimer DianthranilateBis-[4-(3-methyl-5-oxo-2-pyrazolin-1-yl)benzoic acid]Diazo

Part A: Dimer Dianthranilate Bis-Diazotization

To a 500 milliliter 3-neck kettle equipped with mechanical stirrer and athermometer was charged about 19.4 grams (MW=776) dimer esteranthranilate (DEA) precursor, the preparation of which is found inExample 1 of U.S. Pat. No. 6,713,614, the disclosure of which is herebyincorporated by reference herein in its entirety, followed sequentiallywith about 65 grams of glacial acetic acid, about 9.7 grams ofconcentrated sulfuric acid, and about 15.4 grams of deionized water. Thecontents were stirred until everything dissolved. The round bottle wasput in an ice bath and stirred until the temperature was about 3° C. toabout 5° C. To a constant pressure addition funnel was charged about16.2 grams nitrosyl sulfuric acid (NSA, MW=127, 40%-wt in sulfuricacid). The NSA solution was added slowly into the brown DEA solution tomaintain the reaction temperature between about 3° C. to about 10° C.After about 1 hour, the addition was complete and the contents werestirred for another 2 hours. During the 2 hour stir time, aphosphomolybdic acid test (PMA test) was run to insure there was anexcess of NO⁺. The result was positive. Then about 2.0 grams of sulfamicacid was added to react with excess NSA. A PMA test was run after about15 minutes and it showed that all NSA was reacted. At this point the azowas ready to add to the coupler.

Part B: The Coupling of Dimer Dianthranilate Bis-Diazo to4-(3-methyl-5-oxo-2-pyrazolin-1-yl)benzoic acid

Dissolving the 4-(3-methyl-5-oxo-2-pyrazolin-1-yl)benzoic acid: To a 1liter beaker with equipped with a magnetic stir bar was added about 162grams of water, about 14.6 grams of sodium acetate and about 7.1 gramsof NaOH and stirred until everything was dissolved. About 11.1 grams of4-(3-methyl-5-oxo-2-pyrazolin-1-yl)benzoic acid (MW=218) was then addedto the beaker. The solution remained clear.

Adding the Dimer Dianthranilate Bis-Diazo to the4-(3-methyl-5-oxo-2-pyrazolin-1-yl)benzoic acid: The cooled contentsfrom Example 1, Part A above were then slowly added to this solutionallowing the azo coupling to take place. A yellow solids immediatelybegan to precipitate out of solution. The contents were allowed to stirovernight. The yellow solids were collected by filtration, reslurried inabout 200 milliliters of water, and collected by filtration. The solidswere allowed to air dry. The spectral strength of the yellow colorantwas determined using a spectrophotometric procedure based on themeasurement of the colorant in solution by dissolving the colorant intoluene and measuring the absorbance using a Perkin Elmer Lambda 2SUV/VIS spectrophotometer. The spectral strength of the colorant measuredas about 37,882 mL*Absorbance Units per gram at absorption λ_(max).

Example 2 Dimer Dianthranilate Bis-[N-DodecylanilinophenylpyrazoloneCarboxamide]Diazo]

Part A: Dimer Dianthranilate Bis-Diazotization

To a 1 liter 3-neck round bottom flask equipped with a mechanicalstirrer and a thermometer was charged about 21.6 grams (MW=776) of dimerester anthranilate (DEA) precursor, the preparation of which is found inExample 1 of U.S. Pat. No. 6,713,614, the disclosure of which is herebyincorporated by reference herein in its entirety, followed sequentiallywith about 42 milliliters of glacial acetic acid, about 3.6 millilitersof concentrated sulfuric acid, about 4.0 milliliters of deionized waterand about 4.4 milliliters of propionic acid. All dissolved. The roundbottom flask was placed in an ice bath and stirred until the temperaturewas about 3° C. to about 5° C. To a constant pressure addition funnelwas charged about 11.2 milliliters (0.057 moles) of nitrosyl sulfuricacid (NSA, MW=127, 40%-wt in sulfuric acid). The NSA solution was addedslowly into the brown DEA solution to maintain the reaction temperaturebetween about 3° C. to about 10° C. After about 2 hours the addition wascomplete and the contents were stirred for another half hour. Aphosphomolybdic acid test (PMA test) was run to check if the reactioncompleted. The result was negative which suggested the reaction had notcompleted and more NSA was needed. About 1.0 gram of additional NSA wasadded. After about 5 minutes another PMA test was run and the result wasstill negative. About 0.4 gram of NSA was added. After about 15 minutes,the reaction was again checked with a PMA test and the result wasnegative. Another about 0.4 gram of NSA was added and the reaction waschecked with a PMA test. This time the result was positive. The reactionmixture was allowed to stir at about 3° C. to about 5° C. for about 2hours. Then about 0.6 gram sulfamic acid was added to react with excessNSA. A PMA test was run after about 15 minutes and it showed that allNSA was reacted. At this point the azo was ready to add to the coupler.

Part B: The Synthesis of N-Dodecylanilinophenylpyrazolone Carboxamide

To a 500 milliliter 1-neck round bottom flask with equipped with aTeflon® coated stir magnet, condenser and 165° C. oil bath was addedabout 14.5 grams of 4-(3-methyl-5-oxo-2-pyrazolin-1-yl)benzoic acid,about 17.4 grams of dodecylaniline (available from EMF Dottikon), about9.2 grams of PCl₃, and about 165 grams of toluene. The reaction mixturewas refluxed with stirring at 165° C. for about 21 hours at which timethe condenser was removed and a vacuum distillation setup was assembledand the toluene and POCl₃ were distilled off leaving a solid product.The crude solid product was transferred to a 600 milliliter beaker andrecrystallized in about 275 milliliters of ethanol. The solids werecollected by filtration and used without further purification.

Part C: The Coupling of Dimer Dianthranilate Bis-Diazo toN-Dodecylanilinophenylpyrazolone Carboxamide

Dissolving the N-Dodecylanilinophenylpyrazolone Carboxamide: To a 2liter beaker with equipped with a magnetic stir bar was charged about700 grams of deionized. water, about 16.0 grams of acetic acid, andabout 22.2 grams of NaOH. The contents were stirred until completelydissolved. About 700 milliliters of isopropyl alcohol and about 25.2grams of N-dodecylanilinophenylpyrazolone carboxamide from Example 2,Part B was then added and stirred until all was dissolved.

Adding the Dimer Dianthranilate Bis-Diazo to the DissolvedN-dodecylanilinophenylpyrazolone carboxamide: The cooled contents fromExample 2, Part A were added to the beaker containing theN-dodecylanilinophenylpyrazolone carboxamide solution. A yellowprecipitate formed at the beginning of coupling then the solids turnedinto a very viscous liquid. After stirring for one hour the contentswere allowed to settle over night. The top liquid was decanted. Thebottom viscous liquid contained white salt and yellow product. About 700milliliters of deionized water was added to the solids and stirred forabout one hour. The aqueous later was then discarded. The bottom yellowviscous liquid product was dissolved in 700 milliliters of toluene andwashed with water in a separatory funnel. The lower water layer wasdiscarded and top toluene layer was run through a silica plug. Then thetoluene was evaporated yielding a viscous very dark yellow dye. Thespectral strength of the yellow colorant was determined using aspectrophotometric procedure based on the measurement of the colorant insolution by dissolving the colorant in toluene and measuring theabsorbance using a Perkin Elmer Lambda 2S UV/VIS spectrophotometer. Thespectral strength of the colorant measured in toluene as about 9,071mL*Absorbance Units per gram at absorption λ_(max).

Example 3 Menthyl Anthranilate 3-methyl-1-phenyl-2-pyrazoline-5-oneDiazo

Part A: Menthyl Anthranilate Diazotization

To a 150 milliliter 3-neck round bottom flask equipped with a mechanicalstirrer, salt/ice bath, and thermometer was charged about 11.9 grams ofmenthyl anthranilate (MW=275), about 29.7 grams of acetic acid, about5.9 grams of water and about 1.5 grams of concentrated sulfuric acid.The contents were stirred until dissolved while keeping the temperatureof the ice bath at about 0° C. About 16.5 grams of nitrosyl sulfuricacid (NSA MW=127, 40% wt) was slowly through an addition funnelmaintaining the reaction temperature below 3° C. The addition took about32 minutes. The cooled reaction mixture was stirred an additional twohours. A PMA test (to determine excess NO+) was run and the result waspositive indicating the reaction was complete. About 1.8 grams ofsulfamic acid was added (to kill excess NSA) and stirred for 20 minutes.A PMA test confirmed that all excess NSA had been killed. At this pointthe reaction mixture is ready to couple.

Part B: The Coupling of Menthyl Anthranilate Diazo to3-methyl-1-phenyl-2-pyrazoline-5-one

Dissolving the 3-methyl-1-phenyl-2-pyrazoline-5-one: To a 1 liter beakerwith equipped with a magnetic stir bar was added about 100 grams ofwater, about 16 grams of acetic acid and about 22 grams of NaOH andstirred until everything was dissolved. About 7.5 grams of3-methyl-1-phenyl-2-pyrazoline-5-one (MW=174) was then added to thebeaker. The solution remained clear.

Adding the Menthyl Anthranilate Diazo to the Dissolved2-Ethylhexylacetoacetamide: The cooled contents from Example 3, Part Awere then slowly added to this solution allowing the azo coupling totake place. A yellow solids immediately began to precipitate out ofsolution. Additional water was added (about 200 grams) to aid instirring efficiency. The contents were allowed to stir overnight. Theyellow solids were collected by filtration, reslurried in about 200 mlof water, and collected by filtration. The solids were allowed to airdry. The spectral strength of the yellow colorant was determined using aspectrophotometric procedure based on the measurement of the colorant insolution by dissolving the colorant in toluene and measuring theabsorbance using a Perkin Elmer Lambda 2S UV/VIS spectrophotometer. Thespectral strength of the colorant measured in toluene as about 44,992mL*Absorbance Units per gram at absorption λ_(max).

Example 4 The Coupling of Menthyl Anthranilate Diazo toN-Dodecylanilinophenylpyrazolone Carboxamide

Dissolving the N-dodecylanilinophenylpyrazolone carboxamide: To a 4liter beaker with equipped with a magnetic stir bar was added about 200grams of water, about 32 grams of acetic acid, about 44 grams of NaOH,and about 1200 grams of methanol with stirring until everything wasdissolved. About 20.0 grams of N-dodecylanilinophenylpyrazolonecarboxamide from Example 2, Part B above was then added to the beaker. Aprecipitate formed. About 400 additional grams of water and about 1200milliliters of isopropyl alcohol were added to bring all of the contentsinto solution.

Adding the Menthyl Anthranilate Diazo to the Dissolved2-ethylhexylacetoacetamide: The cooled contents from Example 3, Part Aabove were then slowly added to this solution allowing the azo couplingto take place. An orange solids immediately began to precipitate out ofsolution. The contents were allowed to stir overnight. The orange solidswere collected by filtration, reslurried in about 200 milliliters ofwater, and collected by filtration. The solids were allowed to air dry.The spectral strength of the yellow colorant was determined using aspectrophotometric procedure based on the measurement of the colorant insolution by dissolving the colorant in toluene and measuring theabsorbance using a Perkin Elmer Lambda 2S UV/VIS spectrophotometer. Thespectral strength of the colorant measured in toluene as about 32,703mL*Absorbance Units per gram at absorption λ_(max).

Example 5 Preparation of an Ink Base

An ink base was prepared by melting, admixing, and filtering thefollowing ingredients:

43.59 parts by weight polyethylene wax (PE 655®, obtained from BakerPetrolite) of the formula CH₃(CH₂)₅₀CH₃);

19.08 parts by weight stearyl stearamide wax (KEMAMIDE® S-180, obtainedfrom Crompton Corporation);

18.94 parts by weight tetra-amide resin obtained from the reaction ofone equivalent of a C-36 dimer acid (obtained from Uniqema, New Castle,Del.) with two equivalents of ethylene diamine and UNICID® 700 (obtainedfrom Baker Petrolite), a long chain hydrocarbon having a terminalcarboxylic acid group, prepared as described in Example 1 of U.S. Pat.No. 6,174,937, which is hereby incorporated by reference herein in itsentirety;

11.71 parts by weight urethane resin obtained from the reaction of twoequivalents of ABITOL® E hydroabietyl alcohol (obtained from HerculesInc.) and one equivalent of isophorone diisocyanate, prepared asdescribed in Example 1 of U.S. Pat. No. 5,782,966, which is herebyincorporated by reference herein;

6.48 parts by weight urethane resin that is the adduct of threeequivalents of stearyl isocyanate and a glycerol-based alcohol, preparedas described in Example 4 of U.S. Pat. No. 6,309,453, which is herebyincorporated by reference herein in its entirety;

0.20 parts by weight NAUGUARD® 445 antioxidant (obtained from UniroyalChemical Co.).

Thereafter, 600 grams of the ink carrier components as listed above inthe percentages as listed above were added to a 1 liter beaker andheated in an oven at 135° C. until molten. Subsequently, the beaker wasinserted into a heating mantle set to 135° C. and the contents of thebeaker were stirred for 45 minutes. The resulting ink was then filteredthrough a combination of Whatman #3 and 0.2 micron NAE filters andplaced in a Mott filter assembly. Filtration was supported by theaddition of 1 percent by weight FILTER-AID obtained from Fluka Chemika,and proceeded at a temperature of 135° C. until complete after 6 hours.The ink base was poured into molds containing about 31 grams of thecolorless ink base and allowed to cool.

Example 6 Preparation of Ink Containing Colorant

About 30.2 grams of ink base from Example 5 was placed in a 100milliliter beaker equipped with a magnetic stir bar and subsequentlyplaced in a 135° C. oil bath until molten. About 1.26 grams of the dyefrom Example 1, Part B was then added and stirred for about 1 hour. Theyellow colored ink was then poured into an aluminum mold.

Example 7

About 30.4 grams of ink base from Example 5 was placed in a 100milliliter beaker equipped with a magnetic stir bar and subsequentlyplaced in a 135° C. oil bath until molten. About 0.66 grams of the dyefrom Example 3, Part B was then added and stirred for about 1 hour. Theyellow colored ink was then poured into an aluminum mold.

Example 8

About 28.2 grams of ink base from Example 5 was placed in a 100milliliter beaker equipped with a magnetic stir bar and subsequentlyplaced in a 135° C. oil bath until molten. About 0.68 grams of the dyefrom Example 4 was then added and stirred for about 1 hour. The yellowcolored ink was then poured into an aluminum mold.

Example 9 Printing of Ink Samples Containing Colorant

Printed samples of the ink prepared in Examples 6, 7, and 8 weregenerated on HAMMERMILL LASERPRINT® paper using a K Printing Proofer(manufactured by RK Print Coat Instrument Ltd., Litlington, Royston,Heris, SG8 0OZ, U.K.). In this method, the tested inks were melted ontoa printing plate set at 150° C. temperature. A roller bar fitted withthe paper was then rolled over the plate containing the melted ink onits surface. The ink on the paper was cooled, resulting in threeseparated images of rectangular blocks. The most intensely colored blockcontained the most ink deposited on the paper, and was therefore used toobtain the color value measurements. The printed samples were evaluatedvisually.

It will be appreciated that various of the above-disclosed and otherfeatures and functions, or alternatives thereof, may be desirablycombined into many other different systems or applications. Also thatvarious presently unforeseen or unanticipated alternatives,modifications, variations or improvements therein may be subsequentlymade by those skilled in the art which are also intended to beencompassed by the following claims. Unless specifically recited in aclaim, steps or components of claims should not be implied or importedfrom the specification or any other claims as to any particular order,number, position, size, shape, angle, color, or material.

1. A compound of the formula

wherein R is selected from an (i) alkylene group, including substituted and unsubstituted alkylene groups, and wherein hetero atoms either may or may not be present in the alkylene group, (ii) an arylene group, including substituted and unsubstituted arylene groups, and wherein hetero atoms either may or may not be present in the arylene group, (iii) an alkyleneoxy group, including substituted and unsubstituted alkyleneoxy groups, and wherein hetero atoms either may or may not be present in the alkyleneoxy group, (iv) an aryleneoxy group, including substituted and unsubstituted aryleneoxy groups, and wherein hetero atoms either may or may not be present in the aryleneoxy group, (v) a polyalkyleneoxy group, (vi) a polyaryleneoxy group, (vii) a polyarylalkyleneoxy group, (viii) a polyalkylaryleneoxy group, (ix) a heterocyclic group, (x) a silylene group, (xi) a siloxane group, (xii) a polysilylene group, (xiii) or a polysiloxane group, and wherein R′ is selected from (i) an alkyl group, including substituted and unsubstituted alkyl groups, and wherein hetero atoms either may or may not be present in the alkyl group, (ii) an arylalkylene group, including substituted and unsubstituted arylalkylene groups, and wherein hetero atoms either may or may not be present in the arylalkylene group, (iii) an alkylarylene group, including substituted and unsubstituted alkylarylene groups, and wherein hetero atoms either may or may not be present in the alkylarylene group, (iv) an arylalkyleneoxy group, including substituted and unsubstituted arylalkyleneoxy groups, and wherein hetero atoms either may or may not be present in the arylalkyleneoxy group, (v) an alkylaryleneoxy group, including substituted and unsubstituted alkylaryleneoxy groups, and wherein hetero atoms either may or may not be present in the alkylaryleneoxy group, (vi) a heterocyclic group, (vii) a siloxane group, or (viii) hydrogen; wherein X is an oxygen atom; wherein (Y)_(m) and (Z)_(n) are each independently optionally present and where (Y)_(m) and (Z)_(n) are each independently selected from i) a hydrogen atom, (ii) a halogen atom, (iii) a nitro group, (iv) an alkyl group, including substituted and unsubstituted alkyl groups, and wherein hetero atoms either may or may not be present in the alkyl group, (v) an aryl group, including substituted and unsubstituted aryl groups, and wherein hetero atoms either may or may not be present in the aryl group, (vi) an arylalkyl group, including substituted and unsubstituted arylalkyl groups, and wherein hetero atoms either may or may not be present in the arylalkyl group, (vii) an alkylaryl group, including substituted and unsubstituted alkylaryl groups, and wherein hetero atoms either may or may not be present in the alkylaryl group, (viii) a group of the formula

wherein R₇₀ is an alkyl group, including substituted and unsubstituted alkyl groups, and wherein hetero atoms either may or may not be present in the alkyl group, an aryl group, including substituted and unsubstituted aryl groups, and wherein hetero atoms either may or may not be present in the aryl group, an arylalkyl group, including substituted and unsubstituted arylalkyl groups, and wherein hetero atoms either may or may not be present in the arylalkyl group, an alkylaryl group, including substituted and unsubstituted alkylaryl groups, and wherein hetero atoms either may or may not be present in the alkylaryl group, an alkoxy group, including substituted and unsubstituted alkoxy groups, and wherein hetero atoms either may or may not be present in the alkoxy group, an aryloxy group, including substituted and unsubstituted aryloxy groups, and wherein hetero atoms either may or may not be present in the aryloxy group, an arylalkyloxy group, including substituted and unsubstituted arylalkyloxy groups, and wherein hetero atoms either may or may not be present in the arylalkyloxy group, an alkylaryloxy group, including substituted and unsubstituted alkylaryloxy groups, and wherein hetero atoms either may or may not be present in the alkylaryloxy group, a polyalkyleneoxy group, a polyaryleneoxy group, a polyarylalkyleneoxy group, a polyalkylaryleneoxy group, a heterocyclic group, a silyl group, a siloxane group, a polysilylene group, or a polysiloxane group, (ix) a sulfonyl group of the formula —SO₂R₈₀ wherein R₈₀ is a hydrogen atom, an alkyl group, including substituted and unsubstituted alkyl groups, and wherein hetero atoms either may or may not be present in the alkyl group, an aryl group, including substituted and unsubstituted aryl groups, and wherein hetero atoms either may or may not be present in the aryl group, an arylalkyl group, including substituted and unsubstituted arylalkyl groups, and wherein hetero atoms either may or may not be present in the arylalkyl group, an alkylaryl group, including substituted and unsubstituted alkylaryl groups, and wherein hetero atoms either may or may not be present in the alkylaryl group, an alkoxy group, including substituted and unsubstituted alkoxy groups, and wherein hetero atoms either may or may not be present in the alkoxy group, an aryloxy group, including substituted and unsubstituted aryloxy groups, and wherein hetero atoms either may or may not be present in the aryloxy group, an arylalkyloxy group, including substituted and unsubstituted arylalkyloxy groups, and wherein hetero atoms either may or may not be present in the arylalkyloxy group, an alkylaryloxy group, including substituted and unsubstituted alkylaryloxy groups, and wherein hetero atoms either may or may not be present in the alkylaryloxy group, a polyalkyleneoxy group, a polyaryleneoxy group, a polyarylalkyleneoxy group, a polyalkylaryleneoxy group, a heterocyclic group, a silyl group, a siloxane group, a polysilylene group, or a polysiloxane group, or (x) a phosphoryl group of the formula —PO₃R₉₀ wherein R₉₀ is a hydrogen atom, an alkyl group, including substituted and unsubstituted alkyl groups, and wherein hetero atoms either may or may not be present in the alkyl group, an aryl group, including substituted and unsubstituted aryl groups, and wherein hetero atoms either may or may not be present in the aryl group, an arylalkyl group, including substituted and unsubstituted arylalkyl groups, and wherein hetero atoms either may or may not be present in the arylalkyl group, an alkylaryl group, including substituted and unsubstituted alkylaryl groups, and wherein hetero atoms either may or may not be present in the alkylaryl group, an alkoxy group, including substituted and unsubstituted alkoxy groups, and wherein hetero atoms either may or may not be present in the alkoxy group, an aryloxy group, including substituted and unsubstituted aryloxy groups, and wherein hetero atoms either may or may not be present in the aryloxy group, an arylalkyloxy group, including substituted and unsubstituted arylalkyloxy groups, and wherein hetero atoms either may or may not be present in the arylalkyloxy group, an alkylaryloxy group, including substituted and unsubstituted alkylaryloxy groups, and wherein hetero atoms either may or may not be present in the alkylaryloxy group, a polyalkyleneoxy group, a polyaryleneoxy group, a polyarylalkyleneoxy group, a polyalkylaryleneoxy group, a heterocyclic group, a silyl group, a siloxane group, a polysilylene group, or a polysiloxane group; and wherein in (Y)m, m is an integer from about 0 to about 4, and in (Z)n, n is an integer from about 0 to about
 4. 2. A compound according to claim 1, wherein R is a linear alkylene group.
 3. A compound according to claim 1, wherein R is a branched alkylene group.
 4. A compound according to claim 1, wherein R is a saturated alkylene group.
 5. A compound according to claim 1, wherein R is an unsaturated alkylene group.
 6. A compound according to claim 1, wherein R is an unsubstituted alkylene group.
 7. A compound according to claim 1, wherein R is a substituted alkylene group.
 8. A compound according to claim 1, wherein R is an alkylene group wherein hetero atoms selected from oxygen, nitrogen, sulfur, silicon, phosphorus, boron, or mixtures thereof, are present in the alkylene group.
 9. A compound according to claim 1, wherein R is an alkylene group wherein no hetero atoms are present in the alkylene group.
 10. A compound according to claim 1, wherein R is an alkylene group with about 10 carbon atoms.
 11. A compound according to claim 1, wherein R is an alkylene group with about 36 carbon atoms.
 12. A compound according to claim 1, wherein R is


13. A compound according to claim 1, wherein R is


14. A compound according to claim 1, wherein R is


15. A compound according to claim 3, wherein R is a branched alkylene group having 36 carbon atoms which may include unsaturations and cyclic groups.
 16. A compound of the formula


17. A compound of the formula 